Ultrafast Infrared Mechanistic Studies of the Interaction of 1-Hexyne with Group 6 Hexacarbonyl Complexes

Autor:	Charles B. Harris, Elizabeth A. Glascoe, Christine K. Payne, Matthias F. Kling, Jennifer E. Shanoski
Rok vydání:	2005
Předmět:	chemistry.chemical_classification Infrared Chemistry Ligand Organic Chemistry Photodissociation Binding energy Solvation Hexyne Alkyne Photochemistry Inorganic Chemistry Metal visual_art visual_art.visual_art_medium Physical and Theoretical Chemistry
Zdroj:	Organometallics. 24:1852-1859
ISSN:	1520-6041 0276-7333
Popis:	The ultrafast solvation and rearrangement dynamics following the photolysis of M(CO)6 (M = Cr, Mo, W) in terminal alkyne solutions have been investigated. Upon photoinitiated loss of a ligand from the parent metal hexacarbonyl, coordination to an alkyne solvent molecule is followed by rearrangement to a complex that is bound to the terminal alkyne site in a π-bonded fashion. This rearrangement occurs on a time scale that is anticorrelated with the metal−ligand binding energy. A dissociative rearrangement is ruled out for this process in favor of an associative or interchange mechanism. Previous theoretical and experimental studies are examined, and we conclude that the ultimate rearrangement to a vinylidene species is energetically inaccessible at ambient temperatures on the femtosecond to millisecond time scale.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::c29663af8d8fc9e3f4a135aaec250524 https://doi.org/10.1021/om049101m Zobrazit plný text záznamu